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CO-ORDINATION COMPOUNDS

CO­ORDINATION COMPOUNDS

1. INTRODUCTION 2.2 Coordination Compounds

Co-ordination compounds play a vital role. The importance A coordination compound is a molecular compound that
can be realised that life would not have been possible results from the combination of two or more simple molecular
without the existence of chlorophyll (Mg - complex) in plants compounds and retains its identity in the solid as well as in
and haemoglobin (Fe- complex) in the blood of human dissolved state
beings. The study of these compounds will enlarge our
understanding of chemical bonding, physical properties Example
such as magnetic properties of co-ordination compounds
[Cu (NH3)4]SO4 [Cu (NH3)4]2+ + SO 24
2. MOLECULAR OR ADDITION COMPOUNDS
K4 [Fe(CN)6] 4K+ + [Fe (CN)6]4–
When solution containing two or more simple stable
compounds in molecular proportions are allowed to 3. COORDINATION COMPOUNDS
evaporate, crystals of new substances called molecular or
addition compounds are obtained. A Co-ordination compound consists of a ligand, central
Example atom, complex ion, a cation or an anion. The complex ion is
generally written in a square box and the ion (cation or anion)
KCl + MgCl2 + 6H2O KCl.MgCl 2 .6H 2 O is written outside complex ion.
( Carnallite )
eg : [Co (NH3)6] Cl3
CuSO4 + 4 NH3 [Cu(NH 3 ) 4 ]SO 4 [Complex ion] anion
(Tetrammin e copper (II)
sulphate) eg : K4 [Fe (CN)6]
Fe(CN)2 + 4KCN K 4 [Fe(CN )6 ] cation [Complex ion]
( Potassium ferrocyanide) General formula : Ax [MLn]/[MLn]By
where : M is the central metal atom/ion
2.1 Types of Molecular compounds L is the ligand
A is the cation
B is the anion
Some Important Terms pertaining to Coordination Compounds

3.1 Coordination entity

It is the central metal atom or ion which is bonded to a

2.1.1 Double Salt
A double salt is a substance obtained by the combination
of two different salts which crystallize together as a single
substance but ionise as two distinct salts when dissolved
in water. These salts lose their identity in solution i.e. when
dissolved in water they give test of all the ions present in
the salt. eg. Potash alum, Mohr’s salt
FeSO4. (NH4)2 SO4.6H2O o Fe2+ (aq) + 6H2O + 2NH4+ (aq)
(Mohr’s salt) + 2 SO42– (aq)
K2SO4. Al2 (SO4)3 . 24 H2O o2K+ (aq) + 2Al3+ (aq) +
(Potash alum) 4SO43– (aq) + 24H2O
definite number of ions or molecules which is fixed. For
example, in [Co(NH3)6]Cl3, a coordination entity, six ammonia
molecules are surrounded by three chloride ions.
3.2 Central atom/ion
It is the central cation that is surrounded and coordinately
bonded to one or more neutral molecules or negatively
charged ions in a definite geometrical arrangement. For
example, in the complex [Co(NH3)6]Cl3, Co3+ represents the
central metal ion which is positively charged and is
coordinately bonded to six neutral NH3 molecules within
the coordination sphere. The central metal/ion is also
referred to as Lewis acid.
 CO-ORDINATION COMPOUNDS

3.3 Ligands Example K4 [Fe (CN)6]

+ 4–
K4 [Fe (CN)6] o 4 K + [Fe (CN)6]
The ions or molecules bound to the central atom/ion in the
Charge on complex ion = – 4
coordination entity are called ligands. These may be simple
Let charge on Fe = x,
ions such as Cl–, small molecules such as H2O or NH3, larger –
molecules such as H2NCH2CH2NH2. Now charge on cyanide ion (CN ) = –1
Ÿ x + 6 × (–1) = – 4
3.4 Co-ordination Number (C.N) Ÿ x=+ 2
The number of atoms of the ligands that directly bound to Hence oxidation no of Fe = + 2 (or II)
the central metal atom or ion by co-ordinate bonds is known
as the co-ordination number of the metal atom or ion. It is
3.8 Homoleptic and Hetroleptic Complexes
also equal to the secondary valency.
Complexes in which central atom is coordinated with only
Complex Co-ordination numbers one kind of ligands are called homoleptic complexes, eg.
3+
[Co(NH 3 ) 6] . Complexes in which central atom is
K4 [Fe (CN)6] 6 coordinated with more than one kind of ligands are called
– +
[Ag (CN)2] 2 hetroleptic complexes, eg. [Co (NH3)4 Cl2] .
[Pt (NH3)2 Cl2] 4
2–
4. NOMENCLATURE OF COORDINATION
[Ca (EDTA)] 6
COMPOUNDS

3.5 Coordination sphere

The central metal atom or ion and the ligands that are directly
attached to it are enclosed in a square bracket. This had
been called coordination sphere or first sphere of attraction.
It behaves as a single unit because the ligands present in
the coordination sphere are held tightly by the metal ion.
4.1 Nomenclature
Following rules are adopted for naming a complex ion;
(a) Cations are named before anions
(b) Oxidation state (O.S.) of the central metal ion is denoted
by Roman numeral.

Compound Cation O.S. anion

CuCl Copper (I) chloride

CuCl2 Copper (II) chloride
FeCl2 Iron (II) chloride
FeCl3 Iron (III) chloride

(c) The names of ligands are given first followed by the

name of the central metal ion.
3.6 Co-ordination Polyhedron (d) The names of ligands that are anions and ending with

A coordination polyhedron is the spatial arrangement of ‘ide’ are changed to ‘o’

the ligand atoms that are directly attached to the central ‘ite’ are changed to ‘ito’
atom/ion. For example, [Co(NH3)6]3+ is octahedral, [Ni(CO)4]
‘ate’ are changed to ‘ato’
is tetrahedral and [PtCl4]2 is square planar.
(e) Many ligands that are molecules carry the unmodified
3.7 Oxidation Number of Central Metal Atom name
It is defined as the charge that the central metal ion would (f) Positive groups end in – ium
carry if all the ligands are removed along with electron pairs.
It is calculate as follows : hydrazinium.
CO-ORDINATION COMPOUNDS

(g) When there are several ligands of the same kind, we

normally use the prefixes di, tri, tetra, penta and hexa
to show the number of ligands of that type. An
exception occurs when the name of the ligands includes
a number, for example as in ethylenediamine (en). To
avoid confusion in such cases, bis, tris and tetrakis
are used instead of di, tri and tetra, and the name of the
ligand is placed in brackets. EXAMPLE : Write the name of the following compounds ?

e.g. bis (ethylenediamine)

(a) [Fe(NH3)6]Cl3
(h) If anion is a complex, then metal ends with ‘ate’ 2+
(b) [CoCl(NH3)5]
[ Ni(CN) 4 ]2 : tetracyanonickelate (II) ion (c) [CoSO4 (NH3)4] NO3

lead – plumbate (d) [Pt (Py)4] [PtCl4]

(e) [Cr (en)3] Cl3
gold – aurate
zinc – zincate
tin – stannate (f)
silver – argentate
cobalt – cobaltate Sol. (a) Hexaammineiron (III) Chloride

iron – ferrate (b) Pentaamminechloridocobalt (III) ion

(c) Tetraamminesulphatocobalt (III) nitrate
aluminium – aluminate
(d) Tetrapyridineplatinum (II) tetrachloridoplatinate (II)
manganese – manganate (e) Tris (ethylenediamine) chromium (III) chloride
copper – cuprate (f) Tetrakis (ethylenediamine)–P-hydroxo-P-imidodicobalt
(III) ion.
chromium – chromate
platinum – platinate 5. WERNER’S THEORY
(i) If the complex contains two or more metal atoms, it is Werner explained the nature of bonding in complexes and
termed polynuclear. The bridging ligands which link he concluded that in complexes the metal shows two different
types of valency.
the two metal atoms together are indicated by the prefix
P– 5.1 Primary Valency
(j) Ambidentate ligands may be attached through
The primary valency is equal to the oxidation state of the
different atoms
central metal atom or ion. These are non-directional.
M m NO2 (NO2 joined to metal M through
N; it is nitrito-N) EXAMPLE : What are the primary valency of [Co (NH3)6] Cl3
M m ONO (NO2 joined to metal M through & [Co (NH3)6]3+ ?
O; it is nitrito-O) Sol. K4 [Fe (CN)6] : Primary valency is 2.
Similarly, the SCN group may bond M – SCN
(thiocyanato) or M – NCS (isothiocyanato). [Cu (NH3)4] SO4 : Primary valency is 2.

(k) When writing (not naming) the formula of the complex :

* Complex ion should be enclosed by square
brackets and
* Ligands are placed after metal in the alphabetical
order but first negative ligands, then neutral, then
positive.
5.2 Secondary Valency
The number of ligand atoms co-ordinated to the central metal
atom is called secondary valency. These are directional and
so a complex ion has a particular shape.
 CO-ORDINATION COMPOUNDS

be tetrahedral or square planar. This postulate predicted

EXAMPLE : What are the secondary valency of the existence of different types of isomerism in coordination
[Co (NH3)6] Cl3 & K4 [Fe (CN)6] ? compounds.

Sol. In [Co (NH3)6] Cl3 the secondary valency is 6.

K4 [Fe (CN)6] : six ligands are coordinated to Fe. Hence
secondary valency is 6.
The primary valency is satisfied by ions attached to the
complex ions. It is shown by dotted lines. Primary valency
is also known as ionisable valency.
The secondary valency is satisfied by the ligands, they
are non ionisable and are shown by a solid line [Co (NH3)6]
Cl3 can be represented as

EXAMPLES :

Octahedral Square planar Tetrahedral

(C.N = 6) (C.N = 4) (C.N. = 4)

[Cr(CH3)6]3+ [Ni(CN)4]2– [Ni(CO)4]

[Co(NH3)6]3+; [Cr(H2O)6]3+ [Ni(NH3)4] 2+ [CuX4]2– ;[ZnCl4] 2–

An anion present in co-ordination and ionization sphere
is shown by [Fe(CN)6]2–; [Fe(F6)]3– [Cu(NH3)4]2+ [NiX4]2–

Every element tends to satisfy both its primary and [Pt(NH3)6]4+; [PtCl6] 2– X = Cl–, Br–, I–
secondary valencies. A negative ion when present in the
coordination sphere shows a dual behaviour. It may satisfy
Familiar C.N.’s of some common metal ions.
both primary and secondary valencies.
Univalent C.N. Divalent C.N.
+ 2+
Ag 2 V 6
+ 2+
Au 2, 4 Fe 6
+ 2+
Ti 2 Co 4, 6
+ 2+
Cu 2, 4 Ni 4,6
2+
Cu 4, 6
2+
Zn 4
2+
Pd 4
2+
Pt 4
2+
Ag 4

Trivalent C.N. Tetravalent C.N.

3+ 4+
Sc 6 Pt 6
3+ 4+
The ligand which satisfy the secondary valencies are Cr 6 Pd 6
3+
directed toward fixed positions in space. The geometry of Fe 6
the complex ion depends on the coordination number. If the 3
Co +6
metal has coodination number 6, the complex is octahedral, 3+
Os 6
i.e. six positions around the metal are occupied by six donor 3+
atoms of the ligands octahedrally. On the other hand, if the Ir 6
3+
coordination number is 4, the geometry of the complex may Au 4
 CO-ORDINATION COMPOUNDS

6. EFFECTIVE ATOMIC NUMBER (EAN)
Sidgwick proposed effective atomic number abbreviated as
EAN, which is defined as the resultant number of electrons
with the metal atom or ion after gaining electrons from the
donor atoms of the ligands. The effective atomic number
(EAN) generally coincides with the atomic number of next
inert gas in some cases. EAN is calculated by the following
relation :
EAN = Atomic number of the metal – number of electrons
lost in ion formation + number of electrons gained from
the donor atoms of the ligands. (2 × CN)
The EAN values of various metals in their respective
complexes are tabulated below :

Complex Metal (Oxid. state) At. No. of metal Coordination number Effective atomic number

K4 [Fe (CN)6] +2 26 6 (26 – 2) + (6 × 2) = 36 [Kr]

[Cu (NH3)4] SO4 +2 29 4 (29 – 2) + ( 4 × 2) = 35

[Co (NH3)6] Cl3 +3 27 6 (27 – 3) + (6 × 2) = 36 [Kr]

Ni (CO)4 0 28 4 (28 – 0) + (4 × 2) = 36 [Kr]
K2 [Ni(CN)4] +2 28 4 (28 – 2) + (4 × 2) = 34.

7. VALENCE BOND THEORY

COMMON TYPES OF HYBRIDISATION
The bonding in coordination compounds can be explained
by Valence Bond Theory (VBT) since majority of the Coordination Hybridi- Shape Geometry
complexes formed by the transition metals have their d- Number zation
orbitals incomplete. Valence bond takes into account the
2 sp Linear X —A— X
hybridisation of orbitals since penultimate d-orbitals are near
in energy to s and p-orbitals of the outer most shell, various
kinds of hybridization is possible.
VBT makes the following assumption
4 sp 3 Tetrahedron
(i) A number of empty orbitals are available on the central metal
ion which can accomodate electrons donated by the ligands.
The number of empty d-orbitals is equal to the coordination
number of the metal ion for the particular complex.
(ii) The metal orbitals and ligand orbitals overlap to form strong 4 dsp2 Square planar
bonds. Greater the extent of overlapping, more is the stability
of the complex. Different orbitals (s, p or d) hydridize to give
a set of equivalent hybridized orbital which take part in
bonding with the ligands.
(iii) Each ligand donates a pair of electrons to the central metal
ion/atom. 5 sp 3d Trigonal
(iv) The non-bonding metal electrons present in the inner
orbitals do not take part in chemical bonding. or dsp3 bipyramid

(v) If the complex contains unpaired electrons, the complex is

paramagnetic. If it does not contain unpaired electron, the
complex is diamagnetic in nature.
(vi) Under the influence of strong ligand (CN, CO) the electrons 6 d 2 sp 3 Octahedral
can be forced to pair up against the Hund’s rule of
multiplicity. or sp3d2
 CO-ORDINATION COMPOUNDS

The lobes of the eg orbitals (d x 2  y 2 and d z2 ) point along

NOTE :
In d2sp3 hybridisation, the inner d-orbitals (3d orbital)
has been used for bonding, such complexes are called
inner orbital complexes or low spin complexes.
In sp3d2 hybridisation the outer d-orbitals (4d orbital) has
been used for bonding, such complex are called outer
orbital complexes or high spin complexes.
The magnetic moment is given by n ( n  2) BM where
n is the number of unpaired electrons.
the x, y and z axes. the lobes of the t 2g orbitals
(d xy , d xz and d yz ) point in between the axes. The approach
of six ligands along the x, y, z, –x, – y and – z directions will
increase the energy of the d x 2  y2 and d z2 orbitals (which
point along the axes) much more than it increases the energy
of the dxy, dxz and dyz orbitals (which point between the
axes). Thus under the influence of an octahedral ligand field
the d orbitals split into two groups of different energies.

7.1 Limitations of VBT

1. The change in the properties of the ligands and the metal

ions could not be explained.
2. The valence bond theory does not explain why certain
complexes are more labile than other.
3. The VBT does not provide satisfactory explanation for the
existence of inner orbital and outer orbital complexes.
4. The VBT could not explain the colour of complexes

8. CRYSTAL FIELD THEORY
The Crystal Field Theory is more widely accepted than the
valence bond theory. It assumes that the attraction between
the central metal and the ligands in a complex is purely
electrostatic. In the crystal field the following assumptions
are made.
1. Ligands are treated as point charges.
2. There is no interaction between metal orbitals and ligand
orbitals.
3. The d orbitals on the metal all have the same energy (that is
degenerate) in the free atom. However, when a complex is
formed the ligands destroy the degeneracy of these orbitals,
i.e. the orbitals now have different energies.
Ligands which cause only a small degree of crystal field
splitting are termed weak field ligands. Ligands which cause
a large splitting are called strong field ligands. The common
ligands can be arranged in ascending order of crystal field
splitting '.
Spectrochemical Series
I– < Br– <S2–< Cl– < NO3 <F– < OH– < EtOH< oxalate < H2O
(weak field ligands)
< EDTA < (NH3 = pyridine) < ethylenediamine < dipyridyl
< o- phenanthroline < NO 2 < CN– < CO
(strong field ligands)

A pattern of increasing V donation is followed :

Halide donors < O donors < N donors < C donors

The total crystal field stabilization energy is given by

CFSE ( octahedral) 0.4n ( t 2 g )  0.6n ( eg )

where n ( t 2g ) and n ( eg ) are the number of electrons

8.1 Octahedral complexes
In an octahedral complex, the metal is at the centre of the
octahedron, and the ligands are at the six corners. The
directions x, y and z point to three adjacent corners of the
octahedron as shown.
occupying the t2g and eg orbitals respectively. The CFSE is
zero for ions with d0 and d10 configurations in both strong
and weak ligand field. The CFSE is also zero for d 5
configurations in a weak field.
CO-ORDINATION COMPOUNDS

EFFECTS OF CRYSTAL FIELD SPLITTING

CFSE and electronic arrangements in octahedral complexes
Number Arrangement in weak ligand field Arrangement in strong ligand field
of d
electrons t2g eg CFSE Spin only t2g eg CFSE Spin only
'o magnetic moment 'o magnetic moment
Ps (D) Ps (D)

d1 1.73 1.73

d2 2.83 2.83

d3 3.87 3.87

d4 – 0.6 4.90 2.83

d5 – 0.0 5.92 1.73

d6 – 0.4 4.90 0.00

d7 – 0.8 3.87 – 1.8 1.73

d8 – 1.2 2.83 – 1.2 2.83

d9 – 0.6 1.73 – 0.6 1.73

d10 0.0 0.00 0.0 0.00

8.2 Tetrahedral Complexes
A regular tetrahedron is related to a cube. One atom is at the
centre of the cube, and four of the eight corners of the cube
are occupied by ligands as shown.
1.
The directions x, y and z point to the centres of the faces of
the cube. The e orbitals point along x, y and z axes (that is to
2.
the centres of the faces). The t2 orbitals point between x, y
and z axes (that is towards the centres of the edges of the
cube). The direction of approach of the ligands does not
coincide exactly with either the e or the t2 orbitals.
Thus the t2 orbitals are nearer to the direction of the ligands
than the e orbitals. The approach of the ligands raises the
energy of both sets of orbitals. The energy of the t2 orbitals
is raised most because they are closest to the ligands. The
crystal field splitting is the opposite way round to that in
octahedral complexes
The t2 orbitals are 0.4't above weighted average energy of
the two groups (the Bari centre) and the e orbitals are 0.6't
below the average.
The magnitude of the crystal field splitting 't in tetrahedral
complexes is considerably less than in octahedral fields.
There are two reasons for this :
There are only four ligands instead of six, so the ligand field
is only two third the size ; hence the ligand field splitting is
also two third the size.
The direction of the orbitals does not coincide with the
direction of the ligands. This reduces the crystal field
splitting by roughly a further two third.

Thus the tetrahedral crystal field splitting 't is roughly
2/3 × 2/3 = 4/9 of the octahedral crystal field splitting 'o.
9. ORGANOMETALLIC COMPOUNDS
Compounds that contain at least one carbon–metal bond
are called organometallic compounds.
Grignard reagent, RMgX is a familiar example of
organometallic compounds where R is an alkyl group. Diethyl
zinc [Zn(C2H5)2], lead tetraethyl [Pb(C2H5)4], ferrocene
[Fe(C 5H5) 2], dibenzene chromium [Cr(C6H6 )2], metal
carbonyls are other examples of organometallic compounds.
Organometallic compounds may be classified in three classes :
1. Sigma (V) bonded complexes.
2. Pi (S) bonded complexes,
3. Complexes containing both V– and S–bonding
characteristics.
9.1 Sigma bonded complexes
In these complexes, the metal atom and carbon atom of the
ligand are joined together with a sigma bond, i.e., the ligand
contributes one electron and is, therefore, called one electron
donor. Examples are :
(i) Grignard reagent, R–Mg–X where R is an alkyl or aryl group
and X is halogen.
(ii) Zinc compounds of the formula R2Zn such as (C2H5)2Zn.
This was first isolated by Frankland in 1849. Other similar
compounds are (CH3)4Sn, (C2H5)4Pb, Al2(CH3)6, Al2(C2H5)6
and Pb(CH3)4, etc.
9.2 S–bonded
S organometallic compounds
These are the compounds of metals with alkenes, alkynes,
benzene and other ring compounds. In these complexes,
the metal and ligand form a bond that involves the S electrons
of the ligand. Three common examples are Zeise’s salt,
ferrocene and dibenzene chromium. These are shown here :
CO-ORDINATION COMPOUNDS
The number of carbon atoms bound to the metal in these
compounds is indicated by the Greek letter ‘K’ (eta) with a
2 5 6
number. The prefixes K , K and K indicate that 2, 5 and 6
carbon atoms are bound to the metal in the compound.
9.3 V–
V and S–bonded organometallic compounds
Metal carbonyls, compounds formed between metal and
carbon monoxide belong to this class. These compounds
posses both V– and S– bonding. The oxidation state of
metal atoms in these compounds is zero. Carbonyls may be
monomeric, bridged or polynuclear.
In a metal carbonyl, the metal–carbon bond possesses both
the V– and S–character. A V–bond between metal and carbon
atom is formed when a vacant hybrid orbitals of the metal
atom overlaps with an orbital on C atom of carbon monoxide
containing a lone pair of electrons.
– +
Formation of S–bond is caused when a filled orbital of the
metal atom overlaps with a vacant antibonding S* orbital of
C atom of carbon monoxide. This overlap is also called back
donation of electrons by metal atom to carbon. It has been
shown below :
The S–overlap is perpendicular to the nodal plane of V–bond.
In olefinic complexes, the bonding S–orbital electrons are
donated to the empty orbital of the metal atom and at the
same time back bonding occurs from filled orbital of the
metal atom to the antibonding S–orbital of the olefin.
CO-ORDINATION COMPOUNDS

10.1.4 Linkage Isomerism : This type of isomerism occurs

10. ISOMERISM in complex compounds which contain ambidentate ligands

The compounds having same molecular formula but different
structural formula are called isomers.
like NO2 , SCN  , CN  , S2O32 and CO.
For example, [Co(NH3)5NO2] Cl2 and [Co(NH3)5ONO] Cl2
are linkage isomers as NO 2 is linked through N or through
O.
10.1.5 Ligand Isomerism : Some ligands themselves are
capable of existing as isomers, e.g., diamino propane can
exist both as 1, 2-diamino propane (pn) and 1, 3-diamino
propane, also called trimethylene diamine (tn).

10.1 Structural Isomerism

10.1.1 Ionisation Isomerism : This type of isomerism arises

when the coordination compounds give different ions in
solution. For example, there are two isomers of the formula When these ligands (i.e., pn and tn) are associated into
complexes the complexes are isomers of each other. One
Co (NH3)5 BrSO4.
example of isomeric complexes having this ligand is :
[Co(NH 3 ) 5 Br]2   SO 24  [Co(pn)2 Cl2]+ and [Co(tn)2 Cl2]+ ions.
[Co ( NH 3 )5 Br] SO 4
Pentaammin ebromido
( Violet )  cobalt (III) ion 10.1.6 Coordination position isomerism : This type of
isomerism is exhibited by polynuclear complexes by
This isomer gives a white percipitate of BaSO4 with BaCl2 changing the position of ligands with respect to different
solution. metal atoms present in the complex. For example,

[Co( NH 3 )5 SO 4 ]Br [Co(NH 3 ) 5 SO 4 ]  Br 

(Red) Pentaammin esulphato
 cobalt (III) ion

Above isomer gives light yellow precipitate with AgNO3 solution.

10.1.2 Hydrate Isomerism : This type of isomerism arises
when different number of water molecules are present inside
and outside the coordination sphere. This isomerism is best
and
illustrated by the three isomers that have the formula
CrCl3.6H2O.

[Cr(H2O)6]Cl3 , [Cr(H2O)5Cl]Cl2.H2O, and [Cr(H2O)4Cl2]

10.2 Stereo Isomerism
Cl.2H2O are its Hydrate Isomers.
10.1.3 Cordination Isomerism : This type of isomerism is Stereo isomerism is exhibited by those compounds which
observed in the coordination compounds having both have the same position of atoms or groups but these atoms
cationic and anionic complex ions. The ligands are or groups have different arrangement around the central atom.
interchanged in both the cationic and anionic ions to form 10.2.1 Geometrical Isomerism
isomers. An examples is : The complex compounds which have the same ligands in
the co-ordination sphere but the relative position of the
[Pt ( NH3 ) 4 ] [CuCl 4 ] and [Cu ( NH3 ) 4 ] [PtCl 4 ]
Tetraammineplatinum (II) Tetraamminecopper (II)
ligands around the central metal atom is different are called
tetrachloridocuprate (II) tetrachloridoplatinate (II)
 CO-ORDINATION COMPOUNDS

geometrical isomers and the phenomenon is called 3. Mabcd

geometrical isomerism.
10.2.1.1 Geometrical Isomerism in square planar complexes
A square planar complexe having similar ligands at adjacent
positions (90º a part) is called cis - isomer while a square
planar complex having two similar ligands at opposite
positions (180º a part) is called trans-isomer.
1. Ma2b2

Example - 3
Example - 1
Draw the geometrical isomers of [PtClBrpy (NH3)]
Draw the geometrical isomers of [PtCl2(NH3)2]

Sol. Sol.

4. M (AB)2
2. Ma2bc
Example - 4
Draw the geometrical isomers of [Pt(gly)2]

Sol.

Example - 2
Draw the geometrical isomers of [PtCl2(NH3)py]

Sol.
 CO-ORDINATION COMPOUNDS

10.2.1.2 Geomertical Isomerism in octahedral complexes

1. Ma4b2

Example - 7
Draw the geometrical isomers of [Cr(gly)3]

Example - 5 Sol.
+
Draw the geometrical isomers of [CrCl2(NH3)4]

Sol.

5. M(AA)2b2

2. Ma3b3

Example - 8
Draw the geometrical isomers of [CoCl2(en)2]+

Sol.

Example - 6
Draw the geometrical isomers of [RhCl3(py)3]

Sol.

Cis and trans-isomers of [CoIII (en)2 Cl2]+ ion.

(a) Cis-isomer (b) trans-isomer

3. Mabcdef : They form 15 isomers

4. M (AB)3
 CO-ORDINATION COMPOUNDS

6. M (AA)2bc
8. Ma2b2c2
Example - 9
Draw the geometrical isomers of [CoIII (en2) (NH3) (Cl)]2+

Sol.

Example - 11
Draw the geometrical isomers of [PtCl2Br2(NH3)2]
Cis and trans-isomers [CoIII (en2) (NH3) (Cl)]2+ ion
Sol.
7. M(AA)a2b2

Optical Isomerism in octahedral complexes

1. Mabcdef

Example - 10 Example - 12
III +
Draw the geometrical isomers of [Co (en) (NH3)2 Cl2] Draw the optical isomers of
[Pt(Cl)(Br)(I)(py)(NO2)(NH3)]

Sol. Sol.

cis and trans-isomers of [CoIII (en) (NH3)2 Cl2]+

Optical d and 1-forms [PtIV (py) (NH3) (NO2) (Cl) (Br) (I)]0
 CO-ORDINATION COMPOUNDS

2. M (AA)3 5. cis Ma2b2c2

Example - 13
Draw the optical isomers of [Co(en)3]3+

Sol.

Example - 16
Draw the optical isomers of [PtCl2Br2(NH3)2]
3+
The two optical isomeric forms of the complex [Co(en)3]
3. M (AB)3 Sol.

6. cis M(AA)b2c2
Example - 14
Draw the optical isomers of [Cr(gly)3] Example - 17
Draw the optical isomers of [CoCl2 (en) (NH3)2]+
Sol.
Sol.

4. cis M (AA)2b2
7. cis M(AA)2bc
Example - 15
Draw the optical isomers of RhCl2(en)2]+ Example - 18
Draw the optical isomers of [CoCl (en)2 Br]2+
Sol.

Optical active isomers of cis [RhCl2(en)2]+

 CO-ORDINATION COMPOUNDS

(b) Volumetric analysis : Hardness of water can be estimated

11. STABILITY OF COORDINATION COMPOUNDS by titration with EDTA. The metal ions causing hardness,
that is Ca2+ and Mg2+, form stable complexes with EDTA.
The stability of a complex in solution refers to the degree of 2. Metal extraction and purification : Extraction of metals, such
association between the two species involved in the state as silver and gold, is carried out by forming their water soluble
of equilibrium. cyanide complexes with the ore. Pure gold can then be
If we have a reaction of the type : obtained from the solution by addition of zinc. Similarly,
ZZX ML
M + 4L YZZ metals can be purified by formation and then decomposition
4
of their coordination compounds. For example, impure nickel
then the larger the stability constant, the higher the obtained after extraction may be converted into pure nickel
proportion of ML4 that exists in solution. Free metal ions by first converting it to nickel carbonyl and then
rarely exist in the solution so that M will usually be
decomposing.
surrounded by solvent molecules which will compete with
the ligand molecules, L, and be successively replaced by 3. Catalysis : Coordination compounds are used as catalysts
them. For simplicity, we generally ignore these solvent in important commercial processes. For example,
molecules and write four stability constants as follows : (a) The Zeigler-Natta catalyst (TiCl4 and trialkyl aluminium) is
used as a catalyst in the formation of polyethene.
M + L ZZX
YZZ ML K1 = [ML]/[M][L]
(b) The Wilkinson catalyst - RhCl(PPh3 )3 is used in the
ML + L ZZX ML2 K2 = [ML2]/[ML][L] hydrogenation of alkenes.
YZZ
(c) In the Monsanto acetic acid process, various rhodium
ML2 + L ZZX
YZZ ML3 K3 = [ML3]/[ML2][L] complexes, such as [Rh(CO)2I2], [Rh(Cl)(CO)(PPh3)2] or
[Rh(Cl)(CO)2]2, are used as catalyst in the presence of CH3I,
ML3 + L ZZX
YZZ ML4 K4 = [ML4]/[ML3][L] I2 or HI as activator.
where K1, K2, etc., are referred to as stepwise stability 4. Electroplating : Coordination compounds of gold, silver
constants. Alternatively, we can write the overall stability and copper are used as components in the baths used for
constant thus : electroplating articles of other metals with these metals. For
example, in silver plating, K[Ag(CN)2] is used as an
M + 4L YZZ
ZZX ML4 E4 = [ML4]/[M][L]4 electrolyte; in gold plating, K[Au(CN)2] is used as an
The stepwise and overall stability constant are therefore electrolyte; and in copper plating, K3[Cu(CN)4] is used as
related as follows : an electrolyte.

E4 = K1 × K2 × K3 × K4 or more generally, 5. Biological importance : Some important biological

En = K1 × K2 × K3 × K4 ................. Kn
The instability constant or the dissociation constant of
coordination compounds is defined as the reciprocal of the
formation constant.
12. IMPORTANCE AND APPLICATIONS OF
6.
COORDINATION COMPOUNDS
1. Analytical chemistry : The analytical applications of
coordination chemistry are in
(a) Qualitative and quantitative analysis : Metals ions form
colored coordination compounds on reaction with a number
of ligands. These reactions are used for detection of the
metal ions. The colored complexes formed can be used for
the estimation of metals by classical or instrumental methods
such as gravimetry or colorimetry. Some examples are given
as follows :
The presence of iron ions (Fe3+) can be detected by the
addition potassium ferrocyanide solution, which results in
formation of Prussian blue complex.
Fe2+ + K3Fe(CN)6 o KFe[Fe(CN)6] + 2K+
compounds are coordination complexes. For example,
chlorophyll is a complex of Mg2+. This green pigment plays
a vital role in photosynthesis in plants. Similarly,
haemoglobin, the red pigment present in blood, is a
coordination complex of Fe2+ and vitamin B12, an essential
nutrient, is a complex compound of Co3+.
Medicinal uses : Complexing or chelating agents are used
in treating metal poisoning, wherein, the coordination
complex is formed between toxic metal in excess metal and
the complexing agent. For example, EDTA is used in lead
poisoning. EDTA, when injected intravenously into the
bloodstream, traps lead forming a compound that is flushed
out of the body with the urine. Other heavy metal poisonings
that can be treated similarly with chelation therapy are
mercury, arsenic, aluminium, chromium, cobalt, manganese,
nickel, selenium, zinc, tin and thallium. Similarly, chelating
ligands D-penicillamine and desferrioxime B are used for
removal of excess copper and iron, respectively. New potent
drugs are being created using various derivatives of
metallocene. A platinum complex [PtCl2(NH)32] called cis-
platin is used in treatment of cancer.
 CO-ORDINATION COMPOUNDS

14.2 Ligands
13. CO­ORDINATION COMPOUNDS AND
COMPLEX IONS An atom, ion or molecule which can donate alteast a pair of
electrons to the central atom to form a coordinate bond (or
(a) Co-ordination compounds are the compounds in which the
dative linkage) is called as a ligand or a coordinating group.
central metal atom is linked to a number of ligands (ions or
Further in a ligand, the particular atom which actually donates
neutral molecules) by co-ordinate bonds i.e. by donation of the electron pair is called the donor atom.
lone pairs of electrons by these ligands to the central metal
The ligands act as Lewis bases as they donate one or more
atom ion.
electron pair to the central metal atoms or ions witch act as
If a such a compound carries positive or negative charge, it Lewis acids by accepting electrons.
4– 2+
is called a complex ion, e.g. [Fe(CN)6] , [Cu(NH3)4] .
Hence Co-ordination compounds may also be defined as Example
those compounds which contain complex ions, e.g.,
K4[Fe(CN)6], [Cu(NH3)4]SO4, etc. In general, a complex ion
r x
is represented as [MLn] . Where M is the metal ion, L
represents ligands, n is the coordination number of metal 14.2.1 Types of Ligands : Ligands can be classified on the
ion and x is the net charge on the complex. number of lone pair electrons they donate to the central
(b) There are four types of complexes : metal atom or ion.

(i) Cation as complex ion, (carrying a net positive charge) e.g., (a) Monodentate or unidentate ligands : They have one donor
3+ atom that donates only one electron pair to central metal
[Cr (NH3)6] in [Cr(NH3)6]Cl3.
– – – –
atom. eg : F , Cl , Br , H2O, NH3, CN , NO 2 , OH , NH 2 ,
(ii) Anion as complex ion, (carrying a net negative charge) e.g.,
3– – – – – –
[Fe(CN)6] in K3 [Fe(CN)6]. CO, R–OH, SCN , , I , SH , RCOO , RS ,

(iii) Cation and anion both as complex ion. Carrying both +ive
and –ive change. For e.g., [Pt(Py)4] [PtCl4].
(Dimethyl sulfoxide), NH2 NH2 NO 2 ,
(iv) Neutral complex (A complex carrying no net charge) e.g.,
NO3 , S2–, O2– , pyridine.
[Ni(CO)4] etc.
(b) Bidentate ligands : Ligands which have two donor atoms
14. TERMINOLOGY OF CO­ORDINATION and have the ability to link with central metal at two positions
are called bidentate ligands
COMPOUNDS
Example

14.1 Centre of Corrdination

(Central atom/ion or Acceptor atom/ion) :

The cation or neutral atom to which one or more ligands
(1) (2)
(neutral molecules or anions) are attached or coordinated is
the centre of coordination.
The central atom/ion must have empty orbitals as it acts as
an acceptor and thus has to accommodate electron pairs
donated by the donor atom of the ligand. This explains why
the transition metal having empty d-orbitals, form
coordination compounds very readily.
(3) (4)
2+ 3–
For example in the complexes [Ni(NH3)6] and [(CN)6] ,
2+ 3+
Ni and Fe respectively are the central ions.
 CO-ORDINATION COMPOUNDS

(e) Pentadentate ligands

They have five donor atoms

Example :
(5) (6)

(7) (8)

(f) Hexadentate Ligands

They have six donor atoms.

(9) (10) Example :

(c) Tridentate Ligand

The ligands having three donor atoms are called tridentate
ligands.
Example :

(1) (2) 14.2.2 Chelating ligands :

A bidentate or a polydentate ligand is known as a chelating
ligand if on co-ordination it results in the formation of a
(d) Tetradentate ligand cyclic ring structure. The complex thus formed are called
These ligand possess four donor atoms chelates.

Example :

(1) (2)
The chelates containing 5 or 6 membered rings are more
stable. Ligands with larger groups form more unstable rings
than with smaller groups due to steric hinderance.
CO-ORDINATION COMPOUNDS

14.2.3 Ambidentate ligands : 16. STABILITY OF COORDINATION COMPOUNDS

The ligands which have two donor atoms but in forming
complexes only one donor atom is attached to the metal atom
at a given time. Such ligands are called ambidentate ligands.
Example :
IN SOLUTIONS
16.1 In general, higher the charge density on the central ion, the
greater is the stability of its complexes, i.e., the higher value
charge
of radius of the ion , the greater is the stability of its

complexes. Electronegativity of the central ion influences

the stability. The higher the electronegativity of the central
ion, the greater is the stability of its complexes.
16.2. The higher the oxidation state of the metal, the more stable
3+
is the complex. The charge density of Co ion is more than
2+ 3+
Co ion and thus, [Co (NH3)6] is more stable than [Co
2+ 3–
(NH3)6] . Similarly, [Fe (CN)6] is more stable than [Fe
4–
15. CO­ORDINATION NUMBER (C.N) (CN)6] .
The cyano and ammine complexes are far more stable than
The number of atoms of the ligands that directly bound to those formed by halide ions. This is due to the fact that NH3
the central metal atom or ion by co-ordinate bonds is known –
and CN are strong Lewis bases.
as the co-ordination number of the metal atom or ion. It is
2+
also equal to the secondary valency. The complexes of bivalent cations (M ) of 3d-series shown
the following order of stability :
Complex Co-ordination numbers 2+ 2+ 2+ 2+ 2+
Cation Mn Fe Co Ni Cu
K [Fe (CN)6] 6 Ionic size 0.91 0.83 0.82 0.78 0.69 decreases
–
[Ag (CN)2] 2
Stability of increases
[Pt (NH3)2 Cl2]
the complex (Irving William order)
[Ca (EDTA)]2– 6
Chelating ligands form more stable complexes as compared
to monodentate ligands. Greater is the chelation, more is the
stability of complex.